We present a joint theoretical and experimental investigation of the absorption spectra of silver clusters Agn (4n22). The experimental spectra of clusters isolated in an Ar matrix are compared with the calculated ones in the framework of the time-dependent density functional theory. The analysis of the molecular transitions indicates that the s -electrons are responsible for the optical response of small clusters (n8) while the d -electrons play a crucial role in the optical excitations for larger n values.
Bibliographical noteFunding Information:
The authors (M.H., F.R., and D.S.) thank the Centre Informatique National de l’Enseignement Supérieur (CINES) at Montpellier, France (Contract No. 20070822452) and the Pôle Scientifique de Modélisation Numérique (PSMN) at Lyon, France, for generous allocation of computation time. They also gratefully acknowledge J. Lermé for helpful discussions. The authors from Lausanne thank the Swiss National Science Foundation for financial support.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry